JP5502604B2 - Solid drawing material - Google Patents
Solid drawing material Download PDFInfo
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- JP5502604B2 JP5502604B2 JP2010128973A JP2010128973A JP5502604B2 JP 5502604 B2 JP5502604 B2 JP 5502604B2 JP 2010128973 A JP2010128973 A JP 2010128973A JP 2010128973 A JP2010128973 A JP 2010128973A JP 5502604 B2 JP5502604 B2 JP 5502604B2
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- 239000000463 material Substances 0.000 title claims description 83
- 239000007787 solid Substances 0.000 title claims description 82
- 239000001993 wax Substances 0.000 claims description 78
- -1 polypropylene Polymers 0.000 claims description 50
- 239000000049 pigment Substances 0.000 claims description 32
- 239000004743 Polypropylene Substances 0.000 claims description 25
- 229920001155 polypropylene Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 239000004698 Polyethylene Substances 0.000 claims description 21
- 229920000573 polyethylene Polymers 0.000 claims description 21
- 238000000465 moulding Methods 0.000 claims description 20
- 239000012968 metallocene catalyst Substances 0.000 claims description 17
- 239000000314 lubricant Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000012164 animal wax Substances 0.000 claims description 2
- 239000012184 mineral wax Substances 0.000 claims description 2
- 239000012169 petroleum derived wax Substances 0.000 claims description 2
- 235000019381 petroleum wax Nutrition 0.000 claims description 2
- 239000012165 plant wax Substances 0.000 claims description 2
- 238000004040 coloring Methods 0.000 description 27
- 239000003921 oil Substances 0.000 description 14
- 235000019198 oils Nutrition 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002156 mixing Methods 0.000 description 9
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 8
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 8
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 8
- 229940057995 liquid paraffin Drugs 0.000 description 7
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 6
- 239000008116 calcium stearate Substances 0.000 description 6
- 235000013539 calcium stearate Nutrition 0.000 description 6
- 239000004606 Fillers/Extenders Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004200 microcrystalline wax Substances 0.000 description 3
- 229920005606 polypropylene copolymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000870659 Crassula perfoliata var. minor Species 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は固形描画材に関し、詳しくは、描画時の着色量を増加させた硬質の固形描画材に関する。 The present invention relates to a solid drawing material, and more particularly to a hard solid drawing material with an increased amount of coloring during drawing.
従来、固形描画材には、軟質固形描画材と硬質固形描画材とが知られている。軟質固形描画材は、代表的には、顔料とワックスとオイル（油状物質）と必要に応じて体質顔料を含んでなる固形描画材であって、クレヨンやパスと呼ばれるものがこの範疇に属する。一方、硬質固形描画材としては、例えば、顔料と成形用樹脂とワックスと共に、必要に応じて、滑剤、オイル、体質顔料等を含んでなり、所謂プラスチッククレヨンと呼ばれるものが知られている（特許文献１参照）。 Conventionally, soft solid drawing materials and hard solid drawing materials are known as solid drawing materials. The soft solid drawing material is typically a solid drawing material containing pigment, wax, oil (oily substance), and, if necessary, extender pigment, and those called crayon and pass belong to this category. On the other hand, as a hard solid drawing material, for example, a so-called plastic crayon is known which contains a lubricant, oil, extender pigment, etc., if necessary, together with a pigment, a molding resin and wax (patent) Reference 1).
上記軟質固形描画材は、従来、アート紙やコート紙等の描画面に描画すれば、濃色の描画跡を形成することができるが、反面、そのまま、即ち、裸のままでは、手指に付着するので、通常、手指を汚すことのないように、表面に巻紙が巻かれている。これに対して、硬質固形描画材は、裸のままで、手指に持っても、手指に付着することはないが、その代わり、描画跡が薄い、即ち、描画面上に付着して、描画跡を形成する固形描画材の量（以下、着色量という。）が少ないという問題がある。 Conventionally, if the soft solid drawing material is drawn on a drawing surface such as art paper or coated paper, a dark drawing trace can be formed. Therefore, a wrapping paper is usually wound around the surface so as not to get the fingers dirty. On the other hand, the hard solid drawing material remains bare and does not adhere to the finger even if it is held by the finger, but instead, the drawing trace is thin, that is, it adheres on the drawing surface and draws. There is a problem that the amount of the solid drawing material that forms the trace (hereinafter referred to as the coloring amount) is small.
そこで、従来、硬質固形描画材による着色量を増やすために、ロジン樹脂のような粘着性の樹脂を着色量向上剤として固形描画材な配合することが提案されている。しかし、ロジン樹脂は天然樹脂であるので、物性値にばらつきがあり、そこで、これを着色量向上剤として用いるときは、得られる固形描画材が描画跡の濃度特性を含め、安定した描画性に欠けるという問題がある。更に、ロジン樹脂は粘着性を有するので、これを着色量向上剤として配合してなる固形描画材は、その描画跡も幾分、粘着性を有するという問題がある。 Therefore, conventionally, in order to increase the amount of coloring by the hard solid drawing material, it has been proposed to blend an adhesive resin such as rosin resin as a solid amount drawing material as a coloring amount improver. However, since the rosin resin is a natural resin, there are variations in physical property values. Therefore, when this is used as a coloring amount improver, the solid drawing material obtained has stable drawing properties including the density characteristics of the drawing trace. There is a problem of lacking. Furthermore, since the rosin resin has adhesiveness, a solid drawing material obtained by blending this as a coloring amount improving agent has a problem that the drawing trace has some adhesiveness.
本発明は、上述した従来の硬質固形描画材における問題を解決するためになされたものであって、硬質でありながら、高い着色量を有する固形描画材を提供することを目的とする。 The present invention has been made to solve the above-described problems in the conventional hard solid drawing material, and an object thereof is to provide a solid drawing material having a high coloring amount while being hard.
本発明による固形描画材は、少なくとも顔料と、ポリエチレンとポリプロピレンから選ばれる少なくとも１種の成形用樹脂と、第１のワックスと、滑剤と共に、メタロセン触媒を用いて得られたポリプロピレン系重合体からなる第２のワックス（但し、上記第１のワックスはこの第２のワックスを含まない。）を含むことを特徴とする。 The solid drawing material according to the present invention comprises a polypropylene polymer obtained using a metallocene catalyst together with at least a pigment, at least one molding resin selected from polyethylene and polypropylene, a first wax, and a lubricant. It contains a second wax (however, the first wax does not include the second wax).
本発明による固形描画材は、メタロセン触媒を用いて得られたポリプロピレン系重合体からなる第２のワックスを着色量向上剤として有しており、ロジン樹脂に比べて、着色量を一層、高くするのみならず、固形描画材やその描画跡にべたつきを与えない。勿論、メタロセン触媒を用いて得られたポリプロピレン系重合体からなる第２のワックスは、工業製品であるので、物性も安定している。 The solid drawing material according to the present invention has a second wax made of a polypropylene polymer obtained using a metallocene catalyst as a coloring amount improver, and further increases the coloring amount as compared with rosin resin. In addition, it does not give stickiness to the solid drawing material and its drawing trace. Of course, since the second wax made of a polypropylene polymer obtained using a metallocene catalyst is an industrial product, its physical properties are also stable.
本発明による固形描画材は、少なくとも顔料と、ポリエチレンとポリプロピレンから選ばれる少なくとも１種の成形用樹脂と、第１のワックスと、滑剤と共に、メタロセン触媒を用いて得られたポリプロピレン系重合体からなる第２のワックス（但し、上記第１のワックスはこの第２のワックスを含まない。）を含んでなるものである。 The solid drawing material according to the present invention comprises a polypropylene polymer obtained using a metallocene catalyst together with at least a pigment, at least one molding resin selected from polyethylene and polypropylene, a first wax, and a lubricant. The second wax (however, the first wax does not include the second wax).
本発明において、顔料は、描画面上に付着して形成した描画跡における着色剤として機能するものであって、従来、固形描画材において着色剤として用いられているものであれば、いずれでもよく、無機顔料、有機顔料、白色顔料、蛍光顔料等が用いられる。無機顔料としては、例えば、弁柄、群青、紺青、カーボンブラック等を、白色顔料としては、例えば、酸化チタン、亜鉛華、硫化亜鉛、アルミナホワイト等を、有機顔料としては、例えば、フタロシアニン系、アゾ系、キナクリドン系、ジオキサジン系、ジケトピロロピロール系等を挙げることができる。これら顔料は、単独にて、又は２種以上を組み合わせて用いられる。 In the present invention, the pigment functions as a colorant in a drawing mark formed by adhering to the drawing surface, and any pigment may be used as long as it is conventionally used as a colorant in a solid drawing material. Inorganic pigments, organic pigments, white pigments, fluorescent pigments and the like are used. Examples of inorganic pigments include petals, ultramarine blue, bitumen, and carbon black, examples of white pigments include titanium oxide, zinc white, zinc sulfide, and alumina white. Examples of organic pigments include phthalocyanine-based, An azo type, a quinacridone type, a dioxazine type, a diketopyrrolopyrrole type, etc. can be mentioned. These pigments are used alone or in combination of two or more.
顔料の配合量は、その種類にもよるが、発色性や描画性等を考慮すれば、固形描画材の全量において、通常、１〜３０重量％の範囲である。顔料の配合量が固形描画材の全量において、１重量％よりも少ないときは、描画跡の濃度が薄く、実用的でなく、他方、３０重量％よりも多いときは、描画に際して、描画面上における固形描画材の滑りが悪く、滑らかに描画し難い等の問題がある。 The blending amount of the pigment is usually in the range of 1 to 30% by weight with respect to the total amount of the solid drawing material in consideration of the color developability and the drawing property, although depending on the type. When the blending amount of the pigment is less than 1% by weight in the total amount of the solid drawing material, the density of the drawing trace is thin and impractical. On the other hand, when the amount is more than 30% by weight, on the drawing surface during drawing. There is a problem that the solid drawing material is not smoothly slid and is difficult to draw smoothly.
本発明によれば、固形描画材における顔料の配合量は、好ましくは、５〜２５重量％の範囲である。 According to the present invention, the amount of the pigment in the solid drawing material is preferably in the range of 5 to 25% by weight.
本発明においては、上記顔料と共に、必要に応じて、体質顔料が用いられる。体質顔料としては、例えば、タルク、マイカ、カオリンクレー、ベントナイト、雲母、硫酸バリウム、炭酸カルシウム、炭酸マグネシウム、板状アルミナ、硫酸マグネシウム等が用いられる。これら体質顔料は、描画に際して固形描画材の摩耗を促進させる機能を有し、必要に応じて、固形描画材の全量に対して、通常、５０重量％以下の範囲で用いられ、好ましくは、１０〜４０重量％の範囲で用いられる。 In the present invention, an extender is used together with the above-described pigment as necessary. Examples of extender pigments include talc, mica, kaolin clay, bentonite, mica, barium sulfate, calcium carbonate, magnesium carbonate, plate-like alumina, and magnesium sulfate. These extender pigments have a function of accelerating the wear of the solid drawing material at the time of drawing, and are usually used in a range of 50% by weight or less based on the total amount of the solid drawing material, and preferably 10%. Used in the range of ˜40% by weight.
本発明による固形描画材は、ポリエチレンとポリプロピレンから選ばれる少なくとも１種の成形用樹脂を含む。この成形用樹脂は、顔料やワックス等の他の成分を一体にまとめて、硬質固形描画材を形成すると共に、得られる固形描画材に手指に付着しない性質を与える。例えば、低密度ポリエチレンや高密度ポリエチレンは、本発明において、成形用樹脂として好ましく用いられる。 The solid drawing material according to the present invention contains at least one molding resin selected from polyethylene and polypropylene. This molding resin integrates other components such as pigments and waxes together to form a hard solid drawing material and gives the obtained solid drawing material a property that does not adhere to fingers. For example, low density polyethylene and high density polyethylene are preferably used as the molding resin in the present invention.
このような成形用樹脂は、固形描画材に基づいて、通常、１０〜４０重量％の範囲、好ましくは、１５〜３５重量％の範囲で用いられる。固形描画材における成形用樹脂の割合が余りに高いときは、得られる固形描画材が硬すぎて、描画性が悪くなる。しかし、固形描画材における成形用樹脂の割合が余りに低いときは、得られる固形描画材が手指に付着しやすくなるので好ましくない。 Such a molding resin is usually used in the range of 10 to 40% by weight, preferably in the range of 15 to 35% by weight, based on the solid drawing material. When the ratio of the molding resin in the solid drawing material is too high, the obtained solid drawing material is too hard and the drawing property is deteriorated. However, when the ratio of the molding resin in the solid drawing material is too low, the obtained solid drawing material tends to adhere to fingers, which is not preferable.
本発明による固形描画材は、第１のワックスと第２のワックスを含む。本発明において、上記第１のワックスは、描画面における描画跡の定着性の向上のために用いられるものであって、パラフィンワックス、マイクロクリスタリンワックス等の石油系ワックス、カルナウバワックス、ミツロウ、木ロウ、牛脂等の動・植物系ワックス、モンタンワックス等の鉱物系ワックス、ポリエチレンワックス、チーグラー触媒を用いて得られたポリプロピレンワックス等の合成ワックス（但し、後述するメタロセン触媒を用いて得られたポリプロピレン系重合体からなる第２のワックスを除く。）等、従来固形描画材に用いられているワックスが適宜に用いられる。 The solid drawing material according to the present invention includes a first wax and a second wax. In the present invention, the first wax is used for improving the fixability of the drawing trace on the drawing surface, and includes petroleum wax such as paraffin wax and microcrystalline wax, carnauba wax, beeswax, wood. Synthetic waxes such as polypropylene wax obtained by using animal and plant waxes such as wax and beef tallow, mineral waxes such as montan wax, polyethylene wax, and Ziegler catalyst (however, polypropylene obtained using a metallocene catalyst described later) Conventional waxes used in solid drawing materials, such as the second wax made of a polymer, are excluded as appropriate.
本発明による固形描画材において、これら第１のワックスの配合量は、固形描画材の全量に対して、通常、１０〜６０重量％の範囲である。第１のワックスの配合量が固形描画材の全量に対して１５重量％よりも少ないときは、得られる描画跡が描画面上において定着性に劣り、更に、得られる固形描画材が強度に劣るようにもなる。一方、６０重量％よりも多いときは、得られる固形描画材が形成する描画跡の濃度が薄くなるので好ましくない。本発明によれば、好ましくは、ワックスの配合量は、固形描画材の全量に対して、好ましくは、２０〜５０重量％の範囲であり、最も好ましくは、２５〜４５重量％の範囲である。 In the solid drawing material according to the present invention, the blending amount of the first wax is usually in the range of 10 to 60% by weight with respect to the total amount of the solid drawing material. When the blending amount of the first wax is less than 15% by weight with respect to the total amount of the solid drawing material, the obtained drawing trace is inferior in fixability on the drawing surface, and the obtained solid drawing material is inferior in strength. It becomes like. On the other hand, when the amount is more than 60% by weight, the density of the drawing trace formed by the obtained solid drawing material becomes thin, which is not preferable. Preferably, according to the present invention, the blending amount of the wax is preferably in the range of 20 to 50% by weight, and most preferably in the range of 25 to 45% by weight, based on the total amount of the solid drawing material. .
本発明による固形描画材は、上記第１のワックスと共に、必要に応じて、オイルを含んでいてもよい。オイルは、得られる固形描画材に柔らかさを与えて、描画跡の着色性を高めるために用いられる。オイルとしては、流動パラフィン、ミネラルオイル、マシン油、スピンドル油、ヤシ油、ヒマシ油等が好ましく用いられる。例えば、流動パラフィンは、好ましく用いられるオイルの一例である。 The solid drawing material according to the present invention may contain oil, if necessary, together with the first wax. Oil is used to give softness to the resulting solid drawing material and to enhance the colorability of the drawing trace. As the oil, liquid paraffin, mineral oil, machine oil, spindle oil, coconut oil, castor oil and the like are preferably used. For example, liquid paraffin is an example of an oil that is preferably used.
その配合量は、固形描画材の全量に対して、通常、１０重量％以下の範囲であり、好ましくは、１〜５重量％の範囲である。オイルの配合量が固形描画材の全量に対して１０重量％よりも多いときは、得られる固形描画材が強度に劣るのみならず、得られる固形描画材が耐熱性に劣り、また、描画跡がべたつきを有するようになるので好ましくない。 The blending amount is usually in the range of 10% by weight or less, preferably in the range of 1 to 5% by weight, based on the total amount of the solid drawing material. When the blending amount of oil is more than 10% by weight based on the total amount of the solid drawing material, not only the obtained solid drawing material is inferior in strength but also the obtained solid drawing material is inferior in heat resistance, and the drawing trace Is not preferable because it becomes sticky.
本発明による固形描画材は、前記第１のワックスと共に、メタロセン触媒を用いて得られたポリプロピレン系重合体からなる第２のワックスを着色量向上剤として含んでいる。但し、前記第１のワックスはこの第２のワックスを含まない。このポリプロピレン系重合体は、ポリプロピレン又はポリプロピレンを主体とするポリプロピレン共重合体である。
このようなメタロセン触媒を用いて得られたポリプロピレン系共重合体は、低結晶性のポリマーであって、通常、滴点（１７０℃で測定した溶融粘度が５００ｍＰａ・ｓ未満の場合）又は軟化点が８０〜１００℃の範囲にあり、重量平均分子量が５０００〜３００００の範囲にあり、１７０℃で測定した溶融粘度が１５０〜１００００ｍＰａ・ｓの範囲にある。
The solid drawing material by this invention contains the 2nd wax which consists of a polypropylene-type polymer obtained using the metallocene catalyst with the said 1st wax as a coloring amount improving agent. However, the first wax does not include the second wax. This polypropylene polymer is polypropylene or a polypropylene copolymer mainly composed of polypropylene.
The polypropylene copolymer obtained using such a metallocene catalyst is a low crystalline polymer and usually has a dropping point (when the melt viscosity measured at 170 ° C. is less than 500 mPa · s) or a softening point. Is in the range of 80 to 100 ° C., the weight average molecular weight is in the range of 5000 to 30000, and the melt viscosity measured at 170 ° C. is in the range of 150 to 10000 mPa · s.
本発明によれば、このようなメタロセン触媒を用いて得られたポリプロピレン系共重合体からなるワックスとして、市販品であるリコセンＰＰ１３０２やＰＰ１５０２、ＰＰ１６０２（いずれも、クラリアントジャパン（株）製）を用いることができる。 According to the present invention, commercially available products such as Lycocene PP1302, PP1502, and PP1602 (all manufactured by Clariant Japan Co., Ltd.) are used as the wax comprising a polypropylene copolymer obtained using such a metallocene catalyst. be able to.
本発明による固形描画材は、上述したようなメタロセン触媒を用いて得られたポリプロピレン系重合体からなる第２のワックスを１〜１５重量％の範囲で含み、好ましくは、２〜１０重量％の範囲で含む。第２のワックスの配合量が固形描画材の全量に対して１重量％よりも少ないときは、描画跡の着色量を高める効果に乏しく、一方、１５重量％よりも多いときは、手指で描画跡を擦ったときに、手指や描画面を汚すおそれがあるので好ましくない。 The solid drawing material according to the present invention contains in the range of 1 to 15% by weight, preferably 2 to 10% by weight of the second wax composed of the polypropylene polymer obtained by using the metallocene catalyst as described above. Include in range. When the blending amount of the second wax is less than 1% by weight with respect to the total amount of the solid drawing material, the effect of increasing the coloring amount of the drawing trace is poor. On the other hand, when it is more than 15% by weight, drawing with fingers When rubbing a trace, it is not preferable because fingers and the drawing surface may be stained.
更に、本発明による固形描画材は、滑らかに描画跡を形成することができるように、３〜３０重量％、好ましくは、５〜２０重量％の範囲で滑剤を含む。この滑剤としては、例えば、高級脂肪酸金属塩、例えば、ミリスチン酸、パルミチン酸、ステアリン酸等の炭素原子数１２〜２０の高級脂肪酸のアルカリ金属塩やアルカリ土類金属塩が好ましく用いられる。具体例として、例えば、リチウム塩、ナトリウム塩、バリウム塩、カルシウム塩、マグネシウム塩等を挙げることができる。例えば、ステアリン酸カルシウムは、好ましく用いられる滑剤の一例である。また、アルミニウム塩やタルクも滑剤として用いられる。 Furthermore, the solid drawing material according to the present invention contains a lubricant in the range of 3 to 30% by weight, preferably 5 to 20% by weight so that a drawing mark can be smoothly formed. As this lubricant, for example, higher fatty acid metal salts such as alkali metal salts and alkaline earth metal salts of higher fatty acids having 12 to 20 carbon atoms such as myristic acid, palmitic acid and stearic acid are preferably used. Specific examples include lithium salt, sodium salt, barium salt, calcium salt, magnesium salt and the like. For example, calcium stearate is an example of a lubricant that is preferably used. Aluminum salts and talc are also used as lubricants.
本発明による固形描画材は、その製造方法において特に限定されるものではないが、例えば、第１のワックス、成形用樹脂、滑剤、必要に応じて、オイルを混合し、ミキサーにて加熱しながら攪拌、混練し、得られた混合物に顔料と第２のワックスを加え、上記と同じ温度で加熱しながら攪拌、混練し、かくして、得られた混合物を冷却、粉砕し、ペレットとし、これを射出成形機にて適宜の形状に成形して、固形描画材を得ることができる。 The solid drawing material according to the present invention is not particularly limited in its production method. For example, the first wax, a molding resin, a lubricant, and if necessary, oil is mixed and heated in a mixer. Stir and knead, add pigment and second wax to the resulting mixture, stir and knead while heating at the same temperature as above, thus cooling, grinding and pelletizing the resulting mixture and injecting it A solid drawing material can be obtained by molding into an appropriate shape with a molding machine.
本発明による固形描画材は、メタロセン触媒を用いて得られたポリプロピレン系重合体からなる第２のワックスを着色量の向上剤として含んでおり、高い着色量を有し、硬質固形描画材でありながら、描画面上に濃色の描画跡を形成することができ、しかも、固形描画材やその描画跡にべたつきを与えない。 The solid drawing material according to the present invention includes a second wax made of a polypropylene polymer obtained using a metallocene catalyst as a coloring amount improver, has a high coloring amount, and is a hard solid drawing material. However, a dark drawing trace can be formed on the drawing surface, and the solid drawing material and the drawing trace are not sticky.
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例によって何ら限定されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１
表１に示す量にて第１のワックス、成形用樹脂ポリエチレン、滑剤ステアリン酸カルシウム及びオイル流動パラフィンを混合し、ミキサーにて温度１２０℃に加熱しながら攪拌、混練した。得られた混合物に顔料と第２のワックス（着色量向上剤）を加え、上記と同じ温度で加熱しながら攪拌、混練した。得られた混合物を円筒状の成形容器に注入し、冷却し、固化させて、棒状の固形描画材を得た。
Example 1
The first wax, the molding resin polyethylene, the lubricant calcium stearate and the oil liquid paraffin were mixed in the amounts shown in Table 1, and stirred and kneaded while heating to a temperature of 120 ° C. with a mixer. The pigment and the second wax (coloring amount improver) were added to the resulting mixture, and the mixture was stirred and kneaded while heating at the same temperature as described above. The obtained mixture was poured into a cylindrical molding container, cooled and solidified to obtain a rod-shaped solid drawing material.
実施例２〜６
それぞれ表１に示す量にて、顔料１及び／又は顔料２、第１及び第２のワックス（着色量向上剤）、成形用樹脂ポリエチレン、滑剤ステアリン酸カルシウム及びオイル流動パラフィンを用いて、実施例１と同様にして、棒状の固形描画材を得た。
Examples 2-6
Example 1 using Pigment 1 and / or Pigment 2, first and second wax (coloring amount improver), molding resin polyethylene, lubricant calcium stearate and oil liquid paraffin in the amounts shown in Table 1, respectively. In the same manner, a rod-shaped solid drawing material was obtained.
比較例１
第２のワックスを用いることなく、表２に示す量にて顔料、第１のワックス、成形用樹脂ポリエチレン、滑剤ステアリン酸カルシウム及びオイル流動パラフィンを用いて、実施例１と同様にして、棒状の固形描画材を得た。
Comparative Example 1
Without using the second wax, in the same manner as in Example 1, using the pigment, the first wax, the molding resin polyethylene, the lubricant calcium stearate and the oil liquid paraffin in the amounts shown in Table 2, a rod-like solid was used. A drawing material was obtained.
比較例２
実施例３において、着色量向上剤として、第２のワックスに代えて、ロジン樹脂を用いた以外は、同様にして、棒状の固形描画材を得た。
Comparative Example 2
In Example 3, a rod-shaped solid drawing material was obtained in the same manner except that a rosin resin was used instead of the second wax as the coloring amount improver.
比較例３
第２のワックスを用いることなく、表２に示す量にて顔料２、第１のワックス、成形用樹脂ポリエチレン、滑剤ステアリン酸カルシウム及びオイル流動パラフィンを用いて、実施例１と同様にして、棒状の固形描画材を得た。
Comparative Example 3
Without using the second wax, in the same manner as in Example 1, using the pigment 2, the first wax, the molding resin polyethylene, the lubricant calcium stearate and the oil liquid paraffin in the amounts shown in Table 2, A solid drawing material was obtained.
比較例４
実施例３において、第２のワックスに代えて、ポリエチレンワックスを第１のワックスとして用いた以外は、同様にして、棒状の固形描画材を得た。
Comparative Example 4
In Example 3, a rod-like solid drawing material was obtained in the same manner except that polyethylene wax was used as the first wax instead of the second wax.
比較例５
実施例３において、第２のワックスに代えて、メタロセン触媒を用いて得られたポリエチレン系共重合体からなるワックスを第１のワックスとして用いた以外は、同様にして、棒状の固形描画材を得た。
Comparative Example 5
In Example 3, a rod-shaped solid drawing material was prepared in the same manner except that, instead of the second wax, a wax comprising a polyethylene copolymer obtained using a metallocene catalyst was used as the first wax. Obtained.
比較例６
実施例３において、第２のワックスに代えて、チーグラー触媒を用いて得られたポリプロピレンワックスを第１のワックスとして用いた以外は、同様にして、棒状の固形描画材を得た。
Comparative Example 6
In Example 3, a rod-like solid drawing material was obtained in the same manner except that, instead of the second wax, polypropylene wax obtained using a Ziegler catalyst was used as the first wax.
表１及び表２において、各成分の詳細は下記のとおりである。 In Tables 1 and 2, the details of each component are as follows.
（顔料）
顔料１：クラリアントジャパン（株）製赤色顔料ノボパーム・レッドＦ５ＲＫ−ＳＳ
顔料２：（株）トーケムプロダクツ製酸化チタンＴＣＡ−８８８
(Pigment)
Pigment 1: Red pigment Novo Palm Red F5RK-SS manufactured by Clariant Japan
Pigment 2: Titanium Products Titanium Products TCA-888
（成形用樹脂）
ポリエチレン１：日本ポリエチレン（株）製ＰＥ ＬＦ６４０Ｈ
ポリエチレン２：日本ポリエチレン（株）製ＰＥ ＬＪ８０２
(Molding resin)
Polyethylene 1: PE LF640H manufactured by Nippon Polyethylene Co., Ltd.
Polyethylene 2: PE LJ802 manufactured by Nippon Polyethylene Co., Ltd.
（第１のワックス）
パラフィンワックス：台湾蝋品社製５６／５８
マイクロクリスタリンワックス：Ｇｕｊａｒａｔ Ｐａｒａｆｆｉｎｓ社製マイクロ ワックスＤＵ−ＷＡＸ ２
ポリエチレンワックス：ヤスハラケミカル（株）製ネオワックス
ポリエチレン系共重合体：メタロセン触媒を用いて得られたポリエチレン系共重合体から なるワックス、クラリアントジャパン（株）製リコセンＰＥ４２０１
ポリプロピレンワックス：チーグラー触媒を用いて得られたポリプロピレンワックス、三 井化学（株）製ハイワックスＮＰ０５５
(First wax)
Paraffin wax: 56/58 made by Taiwan Wax Co.
Microcrystalline wax: Microwax DU-WAX 2 manufactured by Gujarat Paraffins
Polyethylene wax: Neo-wax polyethylene copolymer manufactured by Yasuhara Chemical Co., Ltd .: Wax made of polyethylene copolymer obtained using a metallocene catalyst, Ricocene PE4201 manufactured by Clariant Japan Co., Ltd.
Polypropylene wax: Polypropylene wax obtained using Ziegler catalyst, high wax NP055 manufactured by Mitsui Chemicals, Inc.
（オイル）
流動パラフィン：三光化学工業（株）製ホワイトミネラルオイル
(oil)
Liquid paraffin: Sanko Chemical Co., Ltd. white mineral oil
（着色量向上剤）
ポリプロピレン系重合体（第２のワックス）：クラリアントジャパン（株）製リコセンＰ Ｐ１６０２
ロジン樹脂：荒川化学工業（株）製ロジンエステルＫＥ−３１１
(Coloring amount improver)
Polypropylene polymer (second wax): Ricosen P P1602 manufactured by Clariant Japan Co., Ltd.
Rosin resin: Rosin ester KE-311 manufactured by Arakawa Chemical Industries, Ltd.
（滑剤）
ステアリン酸カルシウム：正同化学（株）製ＳＣ−Ｐ
(Lubricant)
Calcium stearate: SC-P manufactured by Shodo Chemical Co., Ltd.
（着色量の測定）
水平面上の直交座標系において、予め、重量（Ａ）を測定した画用紙を一定の速度でＹ軸方向の一方向に１０ｃｍ移動させながら、鉛直に保持すると共に、７００ｇの荷重をかけた固形描画材を一定の速度でＸ軸方向に片道４ｃｍの往復動をさせ、かくして、上記画用紙上に上記固形描画材の先端部を連続的に接触させて、画用紙上に矩形状の描画物を形成させた。
(Measurement of coloring amount)
In a rectangular coordinate system on a horizontal plane, a drawing material whose weight (A) is measured in advance is held vertically while moving 10 cm in one direction in the Y-axis direction at a constant speed, and a solid drawing material subjected to a load of 700 g Was reciprocated 4 cm one way in the X-axis direction at a constant speed, and thus the tip of the solid drawing material was continuously brought into contact with the drawing paper to form a rectangular drawing on the drawing paper. .
この後、このように描画された画用紙上の糟（かす）を画筆を用いて取り除いてから、画用紙の重量（Ｂ）を測定し、着色量をＢ−Ａとして求めた。
結果を表１及び表２に示す。
Then, after removing the wrinkles on the drawing paper thus drawn with a paint brush, the weight (B) of the drawing paper was measured, and the coloring amount was determined as B−A.
The results are shown in Tables 1 and 2.
表１及び表２に示すように、実施例１〜５の固形描画材によれば、メタロセン触媒を用いて得られたポリプロピレン系重合体からなる第２のワックスを描画跡の着色量向上剤として含むので、そのような第２のワックスを含まない比較例１の固形描画材と比較して、着色量の増加が著しく、また、着色量向上剤としてロジン樹脂を用いた比較例２の固形描画材と比較しても、着色量の増加が著しい。比較例２の固形描画材は、また、描画跡にはべたつきが認められた。酸化チタンを顔料とする実施例６の固形描画材も、同様に、酸化チタンを顔料とする比較例３の固形描画材と比較して、着色量の増加が著しい。 As shown in Table 1 and Table 2, according to the solid drawing materials of Examples 1 to 5, the second wax composed of the polypropylene polymer obtained using the metallocene catalyst was used as a coloring amount improver for the drawing trace. Therefore, compared with the solid drawing material of Comparative Example 1 that does not contain such a second wax, the coloring amount is remarkably increased, and the solid drawing of Comparative Example 2 using rosin resin as a coloring amount improver. Even when compared with the material, the increase in coloring amount is remarkable. The solid drawing material of Comparative Example 2 was also found to be sticky on the drawing trace. Similarly, the solid drawing material of Example 6 using titanium oxide as a pigment has a remarkable increase in coloring amount as compared with the solid drawing material of Comparative Example 3 using titanium oxide as a pigment.
比較例４の固形描画材は、通常のポリエチレンワックスを用いたものであり、着色量が著しく少ない。比較例５の固形描画材は、メタロセン触媒を用いて得られたポリエチレン系共重合体からなるワックスを用いたものであり、同様に、着色量は著しく少ない。また、比較例６の固形描画材は、チーグラー触媒を用いて得られたポリプロピレンワックスを用いたものであり、同様に、着色量は著しく少ない。
The solid drawing material of Comparative Example 4 uses ordinary polyethylene wax, and the coloring amount is remarkably small. The solid drawing material of Comparative Example 5 uses a wax made of a polyethylene copolymer obtained using a metallocene catalyst, and similarly, the coloring amount is extremely small. Moreover, the solid drawing material of Comparative Example 6 uses a polypropylene wax obtained by using a Ziegler catalyst, and similarly, the amount of coloring is remarkably small.
Claims (4)
A metallocene catalyst, together with at least 1 to 30% by weight of pigment, 10 to 40% by weight of at least one molding resin selected from polyethylene and polypropylene, 10 to 60% by weight of first wax, and 3 to 30% by weight of lubricant 1 to 15% by weight of a second wax comprising a polypropylene-based polymer obtained by using the above (wherein the first wax does not include the second wax) and 10% by weight or less of oil Item 2. The solid drawing material according to Item 1.
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